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Electrochemical reactions powered by renewable electricity are an important means of reducing the carbon footprint of large-scale chemical processes. Here, we investigate the efficient conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), an important building block in the polymer and pharmaceutical industries, using a cheap and abundant nickel-based electrocatalyst. We elucidate the key factors for tuning the chemical selectivity for HMF oxidation over the competing oxygen evolution reaction (OER) at the catalyst surface. We show that the selectivity for HMF oxidation is enhanced by removing trace impurities of iron species as well as adjusting the composition of the alkali hydroxide electrolyte solution. LiOH solution without iron impurities is more favorable for HMF oxidation, whereas CsOH solution with iron species present is more active for the OER and unfavorable for HMF oxidation. Under optimized conditions, HMF oxidation in 1 M LiOH electrolyte solution without iron (pH 14) achieved 98% faradaic efficiency for the production of FDCA. The principles used in this work can be applied to other electrosynthetic reactions, in particular where the OER is the main competing side reaction.

The steady-state photoluminescence (PL) of CsPbBr3 films with varying thicknesses was studied under light-soaking on semiconductive and insulating contacts, showing reversible changes in PL, entirely dependent on the nature of the contact and film thicknesses. The PL at 50–100 nm CsPbBr3 on TiO2 increased, and decreased in thicker layers, with no thickness-dependent PL in CsPbBr3 on glass/Al2O3. These observations are described using a spatial charge distribution model which interprets the migration of Br– and VBr+ under light-soaking as suppressing electron injection into the TiO2 due to upward band bending, enhancing PL at the interface and nonradiative recombination further away from it.

The structural instability of organometal halide perovskites (OHP) is one of the major issues concerning commercialization of perovskite solar cells. Probing this intrinsic instability is one of the major milestones and challenging tasks toward enhancing the lifespan of the material. Here we have incorporated Cs ions into methylammonium lead iodide (MAPbI3) films and studied the thin film structural and optical properties. Incorporation of Cs into MAPbI3 leads to formation of both α-CsPbI3 and ∂-CsPbI3 phases, black and yellow, respectively, as indicated by the evolution of the optical band edge and X-ray diffraction (XRD) spectrum. At a concentration of 20% Cs ions, we observe the existence of a stable α-CsPbI3 phase. Incorporating 59% or more Cs ions yields the yellow phase of CsPbI3, due to alloying of Cs with the MAPbI3 matrix. The structural transformations observed in absorption spectra and XRD are confirmed by low-frequency Raman spectroscopy. The thermally induced structural fluctuations in pure M...

Sb2Se3 has emerged as an important photoelectrochemical (PEC) and photovoltaic (PV) material due to its rapid rise in photoconversion efficiencies. However, despite its binary nature, Sb2Se3 has a complex defect chemistry, which reduces the maximum photovoltage that can be obtained. Thus, it is important to understand these defects and to develop passivation strategies in order to further improve this material. In this work, a comprehensive investigation of the charge carrier dynamics of Sb2Se3 and the influence of sulfur treatment on its optoelectronic properties was performed using time resolved microwave conductivity (TRMC), photoluminescence (PL) spectroscopy and low frequency Raman spectroscopy (LFRS). The key finding in this work is that upon sulfur treatment of Sb2Se3, the carrier lifetime is increased by the passivation of deep defects in Sb2Se3 in both the surface region and the bulk, which is evidenced by increased charge carrier lifetime of TRMC decay dynamics, increased radiative recombination efficiency and decreased deep defect level emission (PL), and improved long-range order in the material (LFRS). These findings provide crucial insights into the defect passivation mechanisms in Sb2Se3 paving the way for developing highly efficient PEC and PV devices.

Funder: Engineering and Physical Sciences Research Council; Id: http://dx.doi.org/10.13039/501100000266, Funder: Cambridge Trust Scholarship, Funder: Robert Gardiner Scholarship, Funder: Royal Society; Id: http://dx.doi.org/10.13039/501100000288, Halide perovskite materials offer an ideal playground for easily tuning their color and, accordingly, the spectral range of their emitted light. In contrast to common procedures, this work demonstrates that halide substitution in Ruddlesden–Popper perovskites not only progressively modulates the bandgap, but it can also be a powerful tool to control the nanoscale phase segregation—by adjusting the halide ratio and therefore the spatial distribution of recombination centers. As a result, thin films of chloride‐rich perovskite are engineered—which appear transparent to the human eye—with controlled tunable emission in the green. This is due to a rational halide substitution with iodide or bromide leading to a spatial distribution of phases where the minor component is responsible for the tunable emission, as identified by combined hyperspectral photoluminescence imaging and elemental mapping. This work paves the way for the next generation of highly tunable transparent emissive materials, which can be used as light‐emitting pixels in advanced and low‐cost optoelectronics.

Sb2Se3 has emerged as an important photoelectrochemical PEC and photovoltaic PV material due to its rapid rise in photoconversion efficiencies. However, Sb2Se3 has a complex defect chemistry, which reduces the maximum photovoltage. Thus, it is important to understand these defects and develop defect passivation strategies in Sb2Se3. A comprehensive investigation of the charge carrier dynamics of Sb2Se3 and the influence of sulfur treatment on its optoelectronic properties is performed using time resolved microwave conductivity TRMC , photoluminescence PL spectroscopy, and low frequency Raman spectroscopy LFR . The key finding in this work is that upon sulfur treatment of Sb2Se3, the carrier lifetime is increased by the passivation of deep defects in Sb2Se3 in both the surface region and the bulk, which is evidenced by increased charge carrier lifetime of TRMC decay dynamics, increased radiative recombination efficiency, decreased deep defect level emission PL , and the emergence of new vibration modes by LFR

In this Letter, we systematically explore the influence of TiO2 thickness with nanometric variations over a range of 20–600 nm on the photovoltaic parameters (open-circuit voltage, short circuit current, fill-factor, and power conversion efficiency) of CH3NH3PbI3-based solar cells. We fabricate several sample libraries of 13 × 13 solar cells on large substrates with spatial variations in the thickness of the TiO2 layers while maintaining similar properties for the other layers. We show that the optimal thickness is ∼50 nm for maximum performance; thinner layers typically resulted in short-circuited cells, whereas increasing the thickness led to a monotonic decrease in performance. Furthermore, by assuming a fixed bulk resistivity of TiO2, we were able to correlate the TiO2 thickness to the series and shunt resistances of the devices and model the variation in the photovoltaic parameters with thickness using the diode equation to gain quantitative insights.

The photovoltage of perovskite solar cells (PSCs) was studied over a wide range of light intensities, showing changes from pristine to light-soaking (LS) conditions, explained using a specific model of spatial charge distribution. Migration of ions and vacancies under photovoltage conditions results in localized charge redistribution manifested as positive charge accumulation at the TiO2 or TiO2–MgO interlayer–perovskite interface, signifying photoinduced interfacial upward band bending. Consequentially, generation of an electrostatic potential (Velec) and an increase in interfacial recombination rate are confirmed. The magnitude and effect of Velec and interfacial recombination on the photovoltage depend on the illumination intensity and on the LS duration. PSCs with mesoporous Al2O3 showed similar changes, validating the role of the compact TiO2. Faster generation and a gradual increase of Velec are apparent under LS, which expresses the constant migration of ions and vacancies toward the interface. The nonrigid TiO2–perovskite interface calls for a vital perspective change of PSCs.

The construction of low cost, printable compatible, solution processed, of high performance, stable solar cells is one of the scientific milestones of the next ten years. The discovery of graphene launched a new era in the materials science, and the research implemented in the exceptional properties of the two-dimensional (2D) materials. The chemical, physical, electrical and mechanical properties of 2D materials match with the requirements that the various building blocks of the third-generation photovoltaics should have in order for these devices to deliver exceptional performance and become attractive alternatives to silicon-based solar cells. The 2D library of materials expands in a very high pace and nowadays includes 150 exotic layered materials. Among them are the transition metal dichalcogenides (2D-TMDs). Recent advances in atomically thin 2D-TMDs (e.g., MoS2, WS2, MoSe2 and WSe2) have introduced numerous promising technologies in nanotechnologies, photonics, sensing, energy storage and solar cells to name few. This chapter highlights the contributions of 2D-TMDs toward the construction of high efficiency and of long lifetime, solution-processed organic and perovskite solar cells.

Summary Drastic changes in open-circuit voltage decay (OCVD) response time in CH 3 NH 3 PbX 3 perovskites have been systematically investigated in order to elucidate the dynamic properties of the interface. Under pre-illumination treatment, the decay times are reduced by orders of magnitude, but if left to rest for sufficient time, the solar cell evolves to its original decay kinetics. In order to explain these observations, we developed advanced modeling of the perovskite solar cell to obtain a realistic description of the immediate vicinity of the interface, including ionic variable concentration and accumulation of holes via degenerate statistics in the space charge region. The results reveal a large amount of majority carriers at the minority carrier extraction contact, assisted by additional ionic charge. The surface band bending related to accumulation gives an electrostatic contribution to the photovoltage in a manner governed by slow dynamics of cations at the electron-selective contact. The modeling of the interface allows us to describe the dynamics of the contact region dominated by surface charging and recombination. These phenomena also play an important role in operation conditions and current-voltage scans of the solar cell.

With solar conversion efficiencies surpassing 20%, organometallic perovskites show tremendous promise for solar cell technology. Their high brightness has also led to demonstrations of lasing and power-efficient electroluminescence. Here we show that thin films of methylammonium lead iodide, prepared by solution processing at temperatures not exceeding 100 °C, exhibit a highly nonlinear intensity-dependent refractive index due to changes in the free-carrier concentration and for femtosecond excitation at higher intensities undergo saturation that can be attributed to the Pauli blocking effect. Nonlinear refractive index and nonlinear absorption coefficients were obtained by the Z-scan technique, performed simultaneously in open- and closed-aperture configurations. Both nanosecond- and femtosecond-pulsed lasers at multiple wavelengths were used in order to distinguish between the mechanisms inducing the nonlinearities. The magnitude and sign of the nonlinear refractive index n2 were determined. For resonan...

In this study we systematically explored the mixed cation perovskite Csx(CH3NH3)1-xPbI3. We exchanged the A-site cation by dipping MAPbI3 films into a CsI solution, thereby incrementally replacing the MA+ in a time-resolved dipping process and analysed the resulting thin-films with UV-Vis, XRD, EDAX, SEM and optical depth-analysis in a high-throughput fashion. Additional in situ UV-Vis and time-resolved XRD measurements allowed us to look at the kinetics of the formation process. The results showed a discontinuity during the conversion. Firstly, small amounts of Cs+ are incorporated into the structure. After a few minutes, the Cs content approaches a limit and grains of δ-CsPbI3 occur, indicating a substitution limit. We compared this cation exchange to a one-step crystallisation approach and found the same effect of phase segregation, which shows that the substitution limit is an intrinsic feature rather than a kinetic effect. Optical and structural properties changed continuously for small Cs incorporations. Larger amounts of Cs result in phase segregation. We estimate the substitution limit of CsxMA1-xPbI3 to start at a Cs ratio x = 0.13, based on combined measurements of EDAX, UV-Vis and XRD. The photovoltaic performance of the mixed cation perovskite shows a large increase in device stability from days to weeks. The initial efficiency of mixed CsxMA1-xPbI3 devices decreases slightly, which is compensated by stability after a few days.

Hybrid methyl-ammonium lead trihalide perovskites are promising low-cost materials for use in solar cells and other optoelectronic applications. With a certified photovoltaic conversion efficiency record of 20.1%, scale-up for commercial purposes is already underway. However, preparation of large-area perovskite films remains a challenge, and films of perovskites on large electrodes suffer from non-uniform performance. Thus, production and characterization of the lateral uniformity of large-area films is a crucial step towards scale-up of devices. In this paper, we present a reproducible method for improving the lateral uniformity and performance of large-area perovskite solar cells (32 cm(2)). The method is based on methyl-ammonium iodide (MAI) vapor treatment as a new step in the sequential deposition of perovskite films. Following the MAI vapor treatment, we used high throughput techniques to map the photovoltaic performance throughout the large-area device. The lateral uniformity and performance of all photovoltaic parameters (V(oc), J(sc), Fill Factor, Photo-conversion efficiency) increased, with an overall improved photo-conversion efficiency of ∼100% following a vapor treatment at 140 °C. Based on XRD and photoluminescence measurements, We propose that the MAI treatment promotes a "healing effect" to the perovskite film which increases the lateral uniformity across the large-area solar cell. Thus, the straightforward MAI vapor treatment is highly beneficial for large scale commercialization of perovskite solar cells, regardless of the specific deposition method.

The high open-circuit potential (Voc) achieved by perovskite solar cells (PSCs) is one of the keys to their success. The Voc analysis is essential to understand their working mechanisms. A large number of CH3NH3PbI3-xClx PSCs were fabricated on single large-area substrates and their Voc dependencies on illumination intensity, I0, were measured showing three distinctive regions. Similar results obtained in Al2O3 based PSCs relate the effect to the compact TiO2 rather than the mesoporous oxide. We propose that two working mechanisms control the Voc in PSCs. The rise of Voc at low I0 is determined by the employed semiconductor n-type contact (TiO2 or MgO coated TiO2). In contrast, at I0 close to AM1.5G, the employed oxide does not affect the achieved voltage. Thus, a change of regime from an oxide-dominated EFn (as in the dye sensitized solar cells) to an EFn, directly determined by the CH3NH3PbI3-xClx absorber is suggested.

The promising solar material Cadmium Telluride (CdTe) is successfully deposited on both plain glass and ITO coated glass substrates. Many variations in composition of the solution used for deposition of the film are made to optimize the deposition conditions. The bandgap calculated from optical transmission studies is found to be a function of the Cd/Te atomic ratio in the film. The atomic ratio in the film is a function of the Cd/Te concentration ratio in the solution used in deposition. Based on several experimental data points an equation involving the Cd/Te atomic ratio in the film and the chemistry of the solution is deduced.

The organic-inorganic hybrid perovskite CH3NH3PbI3 is becoming an interesting material in the field of energy harvesting. This material is one of the cleanest and cheapest components in solar cells which is available in ample amounts. However, most of the previous research work was done on thin film of this material. In the present work we describe the preparation of a powder containing nanoparticles of CH3NH3PbI3 using a sonochemical method. Characterization of the product was done by various methods, such as HRTEM, FTIR, PL, DLS and XRD. The particles were found to be highly crystalline (tetragonal crystal structure), polygonal in shape and having diameters of 10-40nm.

In the pursuit to better understand the mechanisms of perovskite solar cells we performed Raman and photoluminescence measurements of free-standing CH3NH3PbI3 films, comparing dark with working conditions. The films, grown on a glass substrate and sealed by a thin glass coverslip, were measured subsequent to dark and white-light pretreatments. The extremely slow changes we observe in both the Raman and photoluminescence cannot be regarded as electronic processes, which are much faster. Thus, the most probable explanation is of slow photoinduced structural changes. The CH3NH3PbI3 transformation between the dark and the light structures is reversible, with faster rates for the changes under illumination. The results seem to clarify several common observations associated with solar cell mechanisms, like performance improvement under light soaking. More important is the call for solar-cell-related investigation of CH3NH3PbI3 to take the photoinduced structural changes into consideration when measuring and interpreting the results.

Photoconductivity measurements of CH3NH3PbI3 deposited between two dielectric-protected Au electrodes show extremely slow response. The CH3NH3PbI3, bridging a gap of ∼2000 nm, was subjected to a DC bias and cycles of 5 min illumination and varying dark duration. The approach to steady -state photocurrent lasted tens of seconds with a strong dependence on the dark duration preceding the illumination. On the basis of DFT calculations, we propose that under light + bias the methylammonium ions are freed to rotate and align along the electric field, thus modifying the structure of the inorganic scaffold. While ions alignment is expected to be fast, the adjustment of the inorganic scaffold seems to last seconds as reflected in the extremely slow photoconductivity response. We propose that under working conditions a modified, photostable, perovskite structure is formed, depending on the bias and illumination parameters. Our findings seem to clarify the origin of the well-known hysteresis in perovskite solar cells.

Interface engineering through passivating agents, in the form of organic molecules, is a powerful strategy to enhance the performance of perovskite solar cells. Despite its pivotal function in the development of a rational device optimization, the actual role played by the incorporation of interfacial modifications and the interface physics therein remains poorly understood. Here, we investigate the interface and device physics, quantifying charge recombination and charge losses in state-of-the-art inverted solar cells with power conversion efficiency beyond 23% - among the highest reported so far - by using multidimensional photoluminescence imaging. By doing that we extract physical parameters such as quasi-Fermi level splitting (QFLS) and Urbach energy enabling us to assess that the main passivation mechanism affects the perovskite/PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) interface rather than surface defects. In this work, by linking optical, electrical measurements and modelling we highlight the benefits of organic passivation, made in this case by phenylethylammonium (PEAI) based cations, in maximising all the photovoltaic figures of merit.